Jinlong Gong

The electrochemical CO ₂ and CO reduction (CO _x RR) to value‐added multicarbon (C2+) products offers a promising route for sustainable carbon recycling and renewable fuel generation. Although Cu catalysts exhibit unique activity, these single‐metal sites are constrained by linear scaling relations of intermediate adsorption energies, which limits further improvements in selectivity and energy efficiency. Introducing heteroatoms to regulate active‐site coordination provides an effective approach to transcend these limitations. This review describes recent advances in the theoretical design, controllable fabrication, and mechanistic investigation of heteroatomic active sites for CO _x RR toward C2+ products. Theoretical identification for high‐performance sites through descriptor‐based modeling, data‐driven screening, and dynamic simulations is first discussed. Then, the precision synthesis strategies for constructing atomically dispersed, long‐range‐ordered, and interfacial‐confined heteroatomic structures are systematically summarized. Subsequently, mechanistic insights into the promoting effect of heteroatoms, driven by synergistic electronic and geometric modulation, are highlighted, followed by an analysis of future research directions and the key challenges for the industrial implementation of heteroatomic catalysts for CO _x RR. This review provides an integrated perspective linking active‐site design to catalytic performance, offering guidance for the development of next‐generation heteroatomic electrocatalysts for efficient CO _x RR toward the sustainable production of high‐value chemicals.

Chemical looping oxidative propane dehydrogenation (CL‐ODH) as a potentially efficient strategy for propylene production is determined by the gas–solid reaction kinetics. This article describes a macroscopic kinetic model for CL‐ODH over the VCeAl oxygen carrier. Specifically, a comprehensive kinetic model is established to quantify the concurrent pathways of lattice oxygen‐mediated ODH and the catalytic propane dehydrogenation (PDH) over reduced sites as a function of solid conversion. At relatively low temperatures (470–515°C), CL‐ODH gradually evolves from ODH to stable PDH, while ODH has a relatively low activation energy than PDH. It is found that a lower temperature can result in a higher ratio of ODH in comparison with PDH, while higher propane pressure accelerates lattice oxygen depletion and shifts the reaction toward the PDH regime. The macro‐kinetic model could facilitate the industrial scale‐up of CL‐ODH processes.

The electrochemical CO2 reduction reaction (eCO2RR) on CuGa alloys exhibits nonmonotonic selectivity trends that remain mechanistically unexplained. Here, we employ density functional theory (DFT) to investigate three model surfaces (Cu(111), Cu9Ga4(110), CuGa2(110)) spanning the experimentally relevant Ga content range. Ga incorporation progressively strengthens surface oxygen affinity (from 0.47 eV to −0.13 eV) while hydrogen affinity evolves nonmonotonically: Cu9Ga4 binds H slightly more strongly than Cu(111) (−0.04 vs 0.07 eV), while CuGa2 shows the weakest H binding among the three surfaces (0.27 eV). This provides a thermodynamic framework for interpreting selectivity. The free energy landscape analysis identifies *CHO as the pivotal intermediate governing C1 vs C2 branching, with CuGa2 favoring methanol due to diminished *CHO stability despite favorable C–C coupling thermodynamics. For C2 products, the ethylene/ethanol bifurcation at *CH2CHO is controlled by competing C–O cleavage and hydrogenation pathways. Cu9Ga4 exhibits superior ethylene selectivity through a dual geometric mechanism: square-like Cu sites weaken the C–O bond in *CH2CHO (ICOHP: −12.29 vs −12.60 eV on Cu) while sterically suppressing *CH3CHO formation. These findings reveal that Ga regulates eCO2RR selectivity through content-dependent electronic effects and phase-specific geometric effects, offering mechanistic design considerations for CuGa intermetallic catalysts.

Propane dehydrogenation (PDH) requires platinum (Pt) sites that couple high intrinsic activity with propylene selectivity, yet most Pt-based strategies that enhance selectivity rely on electronically modified metallic Pt and can compromise intrinsic rates. This paper describes a discovery that atomically dispersed, cationic Ptδ+ sites can be anchored on zincosilicate *BEA (CIT-6) via ion exchange at framework-derived paired negative charge environments. Transient measurements, (in situ) spectroscopic studies, kinetic analysis, and density functional theory calculations collectively show that Ptδ+ exhibits higher dehydrogenation activity than metallic Pt0, consistent with enhanced C–H bond polarization and facilitated C–H cleavage on electron-deficient centers. As a result, a 0.01 wt. % Ptδ+/CIT-6 catalyst achieves PDH activity comparable to a commercial (mimic) PtSnK/Al2O3 catalyst while using ∼30-fold less Pt. The same design concept extends to zincosilicate CHA and MFI frameworks, establishing framework-anchored positively charged Ptδ+ species as an active motif for Pt-efficient PDH catalysis.

Strongly endothermic reactions are always constrained by thermodynamic equilibrium that necessitates high-temperature operation. This paper describes a co-thermal coupling strategy that integrates two thermodynamic equilibrium-limited processes into a single reaction environment via hydrogen transfer. In this system, the hydrogen generated in situ from endothermic propane dehydrogenation is continuously consumed by simultaneous carbonate decomposition, thereby achieving bidirectional reaction intensification. As a result, the decomposition temperature of calcium carbonate is reduced by approximately 75 °C compared to inert conditions, while the propane dehydrogenation conversion reaches ~120% of the thermodynamic equilibrium value with a propylene selectivity of 97.8% during the continuous regeneration cycles. In situ spectroscopic and kinetic analyses demonstrate a coupled reaction network, where hydrogen transfer promotes carbonate transformation via bicarbonate-related surface intermediates and then follows the reverse water-gas shift pathway. Techno-environmental analysis indicates that this integrated process lowers the energy consumption per ton of propylene by 9.8% and reduces net CO₂ emissions by 18.1% in the base-case industrial simulation, while co-producing propylene and a CaO-containing solid. These findings establish hydrogen-mediated co-thermal coupling as a general strategy for surmounting equilibrium constraints and intensifying energy- and carbon-intensive chemical processes.

Direct hydrogenation of carbon dioxide (CO ₂ ) to acetic acid, a key commodity chemical, offers a sustainable route to valorize greenhouse gases but is plagued by CO ₂ inertness, thermodynamic barriers, and poor selectivity for C-C coupling over competing overhydrogenation. This paper describes the design and synthesis of ultrathin cobalt(II) oxide nanosheets (2 hydrogenation to acetic acid with over 90% selectivity, minimal C ₁ by-products and the highest reported yield under mild conditions, surpassing traditional multistep routes (such as CO ₂ to CO/methanol followed by carbonylation) in cost, efficiency, and atom economy. These two-dimensional structures feature extended terraces that undergo in situ reconstruction in CO ₂ /H ₂ mixtures to a cobalt(II) carbonate hydroxide–like phase, stabilizing Co ²⁺ and generating abundant hydroxyl groups to optimize CO ₂ activation and selective C–C coupling while suppressing over-reduction. In situ characterizations, including electron energy-loss near-edge structure, spatially resolved infrared spectroscopy, and kinetic/isotopic analyses, reveal the reconstructed phase’s role in modulating electron density for superior yields and confirm a formate-coupling mechanism unattainable with conventional catalysts. This study introduces a paradigm for CO ₂ upgrading: harnessing dynamic surface reconstructions and nanoscale morphology to access elusive multicarbon pathways, with implications for sustainable chemical synthesis.

Photocatalytic reaction efficiency is governed by the spin states of active center and reaction intermediates, as it allows selective formation of desired products through spin-dependent reaction pathways. As a representative process, photocatalytic overall water splitting remains limited by water oxidation reaction, where spin-dependent formation of triplet-state O2 is thermodynamically and kinetically unfavorable. This work describes an atom-specific spin modulation strategy by selectively substituting tetrahedral Co2+ with Ni2+ in spinel Co3O4 to form NiCo2O4, which reconstructs the local coordination environment and charge distribution of octahedral Co3+, constructing a high-spin configuration with increased eg occupancy. Under the constraint of external magnetic field, high-spin Co3+ atom generates aligned parallel ·OH radicals, favoring the formation of triplet-state O2 while suppressing singlet byproducts. Meanwhile, the enhanced eg occupancy weakens the adsorption of oxygenated intermediates, lowering the Gibbs free energy barrier of the rate-determining step and accelerating water oxidation. Hence, the NiCo2O4/BiVO4 photocatalyst achieves a water oxidation rate of 148.5 ± 3.7 μmol h−1, which is 5.6 times higher than the pristine BiVO4. Furthermore, it enables near-stoichiometric overall water splitting with a solar-to-hydrogen efficiency of up to 0.309 ± 0.003%. This work underscores the importance of atom-specific spin state regulation to promote spin-polarization-dependent photocatalytic water splitting.

This review describes active-site dynamics, data-driven optimization, LCA, and TEA to evaluate the economic and environmental feasibility of CO ₂ hydrogenation.